Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS5208304 A
Publication typeGrant
Application numberUS 07/772,562
Publication dateMay 4, 1993
Filing dateOct 7, 1991
Priority dateDec 19, 1989
Fee statusLapsed
Publication number07772562, 772562, US 5208304 A, US 5208304A, US-A-5208304, US5208304 A, US5208304A
InventorsRobert M. Waymouth
Original AssigneeBoard Of Trustees, Leland Stanford Junior University
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Stereoregular cyclopolymers and method
US 5208304 A
Abstract
Homogeneous catalyst systems are provided for cyclopolymerization of diolefins, particularly 1,5-hexadiene, which control the stereochemistry, microstructure, and physical properties of the polymers synthesized. The systems comprise homogeneous Ziegler-Natta catalysts based on group 4 metallocenes and methylalumoxane. The cyclopolymers synthesized exhibit different degrees of stereoregularity, which is a function of the polymerization conditions. In addition, the polyolefins can be chiral and optically active. The polymers produced are of high molecular weight and highly flexible.
Images(9)
Previous page
Next page
Claims(12)
It is claimed:
1. A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR6## where C1,C2, and C3 designate respectively the first, second, and third carbon in the ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of:
(a) providing nonconjugated diolefins having the following structural formula: ##STR7## where n is an integer between about 0 and 3 and R1 and R2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R1 is connected to R2 by a chain of atoms; and
(b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C5 R'5)2 MX2, where (C5 R'5) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately atactic.
2. A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR8## where C1,C2, and C3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of:
(a) providing nonconjugated diolefins having the following structural formula: ##STR9## where n is an integer between about 0 and 3 and R1 and R2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R1 is connected to R2 by a chain of atoms; and
(b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C5 R'5)2 MX2, where (C5 R'5) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound; and
(c) controlling the temperature of the diolefins and catalyst system to regulate the trans selectivity in the cyclopolymerization.
3. A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR10## where C1,C2, and C3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of:
(a) providing nonconjugated diolefins having the following structural formula: ##STR11## where n is an integer between about 0 and 3 and R1 and R2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R1 is connected to R2 by a chain of atoms; and
(b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C5 R'5)2 MX2, where (C5 R'5) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately isotactic.
4. A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR12## where C1,C2, and C3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of:
(a) providing nonconjugated diolefins having the following structural formula: ##STR13## where n is an integer between about 0 and 3 and R1 and R2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R1 is connected to R2 by a chain of atoms; and
(b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) an achiral metallocene derivative (C5 R'5)2 MX2, where (C5 R'5) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or hydrocarbyl substituent, M is Zr, Hf, or Ti, and X is any uninegative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the substituents of C1 and C3 of the monomers in the polymers synthesized are predominately in the trans position.
5. A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR14## where C1,C2, and C3 designate respectively the first, second, and third carbon in the ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of:
(a) providing nonconjugated diolefins having the following structural formula: ##STR15## where n is an integer between about 0 and 3 and R1 and R2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R1 is connected to R2 by a chain of atoms; and
(b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula:
R"(C5 (R')4)2 MX2 
wherein (C5 (R')4) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C5 (R')4) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately atactic.
6. A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR16## where C1,C2, and C3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of:
(a) providing nonconjugated diolefins having the following structural formula: ##STR17## where n is an integer between about 0 and 3 and R1 and R2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R1 is connected to R2 by a chain of atoms;
(b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula:
R"(C5 (R')4)2 MX2 
wherein (C5 (R')4) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C5 (R')4) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound; and
(c) controlling the temperature of the diolefins and catalyst system to regulate the trans selectivity in the cyclopolymerization.
7. A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR18## where C1,C2, and C3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of:
(a) providing nonconjugated diolefins having the following structural formula: ##STR19## where n is an integer between about 0 and 3 and R1 and R2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R1 is connected to R2 by a chain of atoms; and
(b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula:
R"(C5 (R')4)2 MX2 
wherein (C5 (R')4) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C5 (R')4) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the polymers synthesized are predominately isotactic.
8. A method of preparing polymers formed of monomer moieties, substantially each monomer having the following structural formula: ##STR20## where C1,C2, and C3 designate respectively the first, second, and third carbon int he ring of each monomer, where n is an integer from 0 to about 3 and m is a positive number up to about 10,000, comprising the step of:
(a) providing nonconjugated diolefins having the following structural formula: ##STR21## where n is an integer between about 0 and 3 and R1 and R2 are hydrogens or hydrocarbyl substituents between 1 and 20 carbons in length, including cyclic structures where R1 is connected to R2 by a chain of atoms; and
(b) adding a soluble catalyst system to the diolefins, said catalyst system consists essentially of (i) a chiral stereorigid metallocene described by the formula:
R"(C5 (R')4)2 MX2 
wherein (C5 (R')4) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C5 (R')4) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide and (ii) an aluminum compound wherein the substituents of C1 and C3 of the monomers in the polymers synthesized are predominately in the trans position.
9. The method as defined in either claim 1, 2, 3 or 4 wherein >90% of the monomer moieties that form the polymers comprise of cyclized nonconjugated diolefins.
10. The method as defined in either claim 5, 6, 7 or 8 wherein >90% of the monomer moieties that form the polymers comprise of cyclized nonconjugated diolefins.
11. The method as defined in claim 9 wherein the aluminum compound is selected from the group consisting of alumoxane and methylalumoxane.
12. The method as defined in claim 10 wherein the aluminum compound is selected from the group consisting of alumoxane and methylalumoxane.
Description

This is a division of application Ser. No. 452,721, filed Dec. 19, 1989, now U.S. Pat. No. 5,104,956.

FIELD OF THE INVENTION

The present invention relates to high molecular weight stereoregular cyclopolymers and particularly to catalyst systems for cyclopolymerization of non-conjugated diolefins.

BACKGROUND OF THE INVENTION

Cyclopolymerization of 1,5-hexadiene was first reported by Marvel and Stille, and further investigated by Makowski. See Marvel, C.S. et al., "Intermolecular-Intramolecular Polymerization of α-Olefins by Metal Alkyl Coordination Catalysts", J. Am. Chem. Soc., 1958, 80, 1970 and Makowski, H.S. et al., "1,5-Hexadiene Polymers, I., Structure and Properties of Poly 1-5 Hexadiene", J. Polymer Sci., Part A. 1964, 2, 1549. Both studies utilized heterogeneous Ziegler-Natta catalysts which promote a special type of addition polymerization referred to as coordination polymerization. Marvel and Makowski both reported low activities and incomplete cyclization of the diolefin. More recently, Cheng reported the cyclopolymerization of 1,5-hexadiene using a catalyst system of diethylaluminum chloride and titanium trichloride. 13 C-NMR analysis of the resulting polymer indicated complete cyclization and an approximate 1:1 ratio of tran- and cis-fused cyclopentane rings in the polymer. Cheng et al., "13 C-NMR Characterization of Poly(1,5-hexadiene)", J. Appl. Polym. Sci., 1988, 35, 825.

One of the special features of Ziegler-Natta catalysts is the stereochemistry associated with polymerization. Radical- and cationic-chain polymerization of monosubstituted olefins lead to products having random stereochemical configuration, referred to as atactic polymers. Regular stereoisomers are possible, and some Ziegler-Natta catalysts promote formation of stereoregular polymers. Isotactic polymers of α-olefins are those having the same stereochemistry at each asymmetric carbon and syndiotactic polymers are those where the configuration alternates regularly down the chain. For instance, Ziegler-Natta catalysts have produced isotactic, syndiotactic and atactic polypropylenes.

Bis(cyclopentadienyl) bis(phenyl) titanium/ methylalumoxane was reported as the first homogeneous catalyst system to influence and control the stereochemistry of propylene polymerization. Ewen, J.A., "Mechanisms of Stereochemical Control in Propylene Polymerizations with Soluble Group 4B Metallocene/ Methylalumoxane Catalysts", J. Am. Chem. Soc., 1984, 106, 6355. More recently, it was reported that homogeneous zirconium catalysts produced isotactic polypropylene and polybutene. Kaminsky, W., et al., "Polymerization of Propene and Butene with a Chiral Zirconocene and Methylalumoxane as Cocatalyst", Angew. Chem. Int. Ed. Engl., 1985, 24, 507.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide homogeneous catalyst systems for cyclopolymerization of diolefins particularly 1,5-hexadiene, which control the stereochemistry, microstructure, and therefore the physical properties of the polymers synthesized.

It is a further object of the present invention to provide polymers that have a combination of useful physical properties: high flexibility combined with high strength and crystallinity.

It is a further object of this invention to prepare chiral and optically active polyolefins. Unlike polypropylene, the cyclopolymers of the invention are chiral.

These and other objects are provided by the present invention.

In one aspect of the present invention, polymeric compounds are provided having the structure ##STR1## where C1,C2, and C3 designate respectively the first, second, and third carbon in the ring of each monomer moiety, where n is an integer from 0 to about 3 and m is an integer between about 1 and 10,000, and where the substituents to C1 and C3 are predominately in the trans or cis position.

These compounds are generally of high molecular weight, highly flexible and durable. These compounds, in particular those where the substituents to C1 and C3 are trans, are chiral and can be made optically active through selection of optically active catalyst precursors.

In another aspect of the invention, catalyst systems for the cyclopolymerization of non-conjugated diolefins into high molecular weight stereoregular polymers are provided. One system consists of a catalyst system for the cyclopolymerization of non-conjugated diolefins including diallyldimethylsilane into high molecular weight polymers comprising: (a) an achiral metallocene derivative (C5 R5)2 MX2, where (C5 R'5) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is a hydrogen or a hydrocarbyl substituent, M is Hf, Ti, or Zr, and where X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide; and (b) an aluminum compound.

The second system consists of a catalyst system for the cyclopolymerization of non-conjugated diolefins including diallydimethylsilane into high molecular weight polymers comprising: (a) a chiral stereorigid metallocene described by the formula:

R"(C5 (R')4)2 MX2 

wherein (C5 (R')4) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R' is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C5 (R')4) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide; and (b) an aluminum compound.

In another further aspect of the invention, a method for preparing high molecular weight stereoregular cyclopolymers from non-conjugated diolefins is provided. The method consists of promoting and controlling cyclopolymerization by use of the said catalyst systems and regulating the temperature and other parameters of the reaction. The method can be employed to produce either the atactic or isotactic forms of the inventive compounds in trans or cis configuration with varying degrees of stereoregularity.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Compounds in accordance with the invention have the structure illustrated in Formula I, below. ##STR2## where C1,C2, and C3 designate respectively the first, second, and third carbon in the ring of each monomer moiety, where n is an integer from 0 to about 3 and m is an integer between about 1 and about 10,000, and where the substituents to C1 and C3 are predominately in the trans or cis position.

As is apparent, C1 and C3 of each repeating unit of the polymer are chiral centers and the polymers, in contrast to stereoregular poly-α-olefins, are chiral polymers. The inventive compounds can be prepared with a range of molecular weights with oligomers as low as m =1, to high polymers with m >10,000, m also referred to as the degree of polymerization. In addition, as will be further described below, the compounds are stereoregular with respect to the cis-trans relationship C1 and C3 in the repeating units, as well as with regard to the relative stereochemistry between the carbocyclic rings. Furthermore, the inventive compound polymers are either predominately atactic or isotactic.

The compounds are derived from the cyclopolymerization of diolefins. The overall reaction from initial reactants to formation of the desired cyclopolymer is generally illustrated by Reaction Scheme I below. ##STR3##

As is apparent, there is a direct relationship between the length of the diolefin reactant and the size of the ring in the cyclopolymer. Thus, 1,5-hexadiene, where n=0, produces cyclopentane; 1,6-heptadiene, where n=1, produces cyclohexane; and so forth. In addition, by utilizing substituted diolefins reactant, cyclopolymers with substituted rings are produced. As an example, 3-methyl-1,5-hexadiene has been cyclopolymerized into cyclomethylpentane with the methyl attached to the C or C of the pentane ring. Furthermore, it is contemplated that heterocyclic polymers are possible. For instance, diallydimethysilane is expected to form poly(1,3-methylene-5,5-dimethylsilacyclohexane).

The inventive compounds are synthesized by utilizing either of two novel catalyst systems, as will now be described. The first system consists essentially of a catalyst for the cyclopolymerization of non-conjugated diolefins including diallyldimethylsilane into high molecular weight polymers comprising: (a) an achiral metallocene derivative (C5 R'5)2 MX2, where (C5 R'5) is a substituted or nonsubstituted cyclopentadienyl ligand, R' is hydrogen or a hydrocarbyl substituent, M is Hf, Ti, or Zr, and where X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide; and (b) an aluminum compound. The second system consists essentially of a catalyst system for the cyclopolymerization of non-conjugated diolefins including diallydimethylsilane into high molecular weight polymers comprising: (a) a chiral stereorigid metallocene described by the formula:

R"(C5 (R')4)2 MX2 

wherein (C5 (R')4) is a cyclopentadienyl or substituted cyclopentadienyl ring, including indenyl and tetrahydroindenyl rings; each R, is a hydrogen or hydrocarbyl radical having from 1 to 20 carbon atoms; R" is an organic or inorganic group providing a structural bridge between the two (C5 (R')4) rings imparting stereorigidity to the said catalyst; M is Zr, Hf, or Ti; and X is any uni-negative ligand including a halide, hydrocarbyl, alkoxide or amide; and (b) an aluminum compound.

In general, a variety of techniques to carry out polymerization are known. Two such techniques were employed to synthesize the inventive compounds. In one method, referred to as bulk polymerization, prescribed amounts of diolefin reactants and catalysts were mixed whereas in the slow monomer addition method, reactant was added slowly over a period of time. The bulk and slow addition techniques are described in greater detail in Method I and Method II below.

The specific parameters and conditions under which Methods I and II were applied are set forth in Table I below as well as are the results from the analysis of the polymers formed.

METHOD I

In a 100 ml schlenk with stirring bar was placed 1,5-hexadiene and the system thermostatted at the desired temperature by an external cooling-heating bath. The metallocene was weighed in a NMR tube, transferred into a 10 ml schlenk, and methylalumoxane added: a lemon-yellow Cp2 ZrMe2 or yellow-orange EBIZrCl2 gel was obtained. After 5 minutes aging, the desired amount of catalyst was transferred into the schlenk containing the diolefin, with vigorous stirring. The polymerization was stopped with CH3 OH, the polymer washed with HCl/CH3 OH and then CH3 OH, filtered and dried overnight at 0.02 Torr. With this procedure, conversions were quantitative, but temperature control was impossible and the resulting polymer was poorly soluble in CDCl3.

METHOD II

In a three-neck 250 ml round bottomed flask equipped with stopcock, stirring bar and dropping funnel with side arm were placed 50 ml toluene, the system brought to the polymerization temperature and the catalyst added. With vigorous stirring, a solution of 5 ml 1,5-hexadiene in 50 ml toluene was added dropwise over 30 minutes. The mixture was allowed to stir for an addition 30 minutes, then quenched with 2 ml CH3 OH and stirred until no more gas evolution was observed. The volatiles were removed in vacuo at 50 C. and checked by gas chromatography. Only the peaks due to CH3 OH, hexadiene and toluene were observed. Conversions were obtained both by polymer weighing and gas chromatography. The polymers were isolated as in the procedure set forth in Method I. The polymers can be fractionated by boiling solvent extraction in the usual manner.

                                  TABLE I__________________________________________________________________________Cyclopolymerization of 1,5-hexadiene                   Toluene                        Conver-                              TransRun #    Metallocene      μ mol          Al/Mt              T (C.)                   (ml) sion (%)                              (%) (a)                                  Method__________________________________________________________________________1   Cp2 ZrCl2      4.8 2300               21  100  11.1  80  II2   Cp2 ZrMe2      14.3          1300               22 (b)                   --   100.0                              78 (c)                                    I3   Cp2 ZrMe2      4.8 2400               22  100  25.0  83  II4 (d)    Cp2 ZrMe2      6.7 2500                0  100  56.0  89  II5 (e)    Cp2 ZrMe2      14.3          1300              -78   50  0.6   95  (f)6   EBIZrCl2      4.8 2400               22  100  81.4  64  II7   EBIZrCl2      3.2 3000               55  100  98.0  61  II__________________________________________________________________________ Conditions: 1,5hexadiene 5 ml, polymerization time 1 hour. (a) From C4, 5 ct/t ratio (b) temperature runaway 5 (c) CHCl3 soluble fraction (d) 4 hours, 30 (e) 7 hours (f) catalyst added to the toluene/monomer solution at -78 C.
Results and Analysis

Presented in Table I are results for the cyclopolymerization of 1,5-hexadiene in the presence of catalysts derived from Cp2 ZrX2 or EBIZrX2 derivatives (Cp=cyclopentadienyl, X=Cl, Me; EBI=ethylenebisindenyl) and methylalumoxane. Mehtylalumoxane (avg. mol. wt.: 1400 g/mol) was obtained from Sherex as a 30% solution in toluene and was used as received. Cyclopolymerization of 1,5-hexadiene in toluene solution with catalysts systems containing Cp2 ZrCl2 or Cp2 ZrMe2 proceeded with conversions of 11 and 25% after 1 hour to give a high molecular weight solid polymer. H-NMR analysis yielded no detectable end groups. Resonances corresponding to uncyclized monomer units were barely detectable by 1 H or 13 C-NMR; thus, under these conditions, greater than 99% cyclization had taken place. Polymerization in bulk monomer (Method I) proceeded with 100% conversion after 1 hour; in this case, a fraction of the polymer was insoluble in chloroform, suggesting that some crosslinking may have occurred. However, the chloroform soluble fractions contained no detectable uncyclized monomer units in the polymer.

By way of comparison, polymerization of 1-hexene under the same conditions with Cp2 ZrMe2 proceeded with similar conversion of monomer but yielded only low molecular weight oligomers (Dp=6). The molecular weight of the oligmers was determined by end group analysis using 1 H-NMR. Thus, under similar conditions, 1,5-hexadiene produces a much higher molecular weight polymer than 1-hexene. Since molecular weight is determined by the relative rates of propagation and termination and similar conversions were obtained with both monomers, the higher molecular weight can be attributed to a lower termination rate in the polymerization of 1,5-hexadiene. A possible origin of this result is the strain energy of the methylene cyclopentane endgroups relative to 1,1-disubstituted olefin endgroups. If the rate of β-hydrogen elimination is sensitive to the strain energy of the liberated olefin, then lower termination rates for the cyclopolymerization might be expected. Consistent with this analysis, cyclopolymerization of 1,6-heptadiene with Cp2 ZrMe2 yielded only oligomers (Dp=17). Although the propagation rate of 1,6-heptadiene is expected to be slightly lower than that of 1,5-hexadiene, the lower molecular weight in this case is consistent with the lower strain energy of methylenecyclohexane (1.0 kcal/mol) relative to methylenecyclopentane (6.3 kcal/mol). See Schleyer et al., "The Evaluation of Strain Energy in Hydrocarbons. The Strain of Adamantane and Its Origin", J. Am. Chem. Soc.. 1970, 98, 2377.

Stereochemistry

Catalyst assisted cyclopolymerization of 1,5-hexadiene is depicted in Formula II. ##STR4##

Formula III represents an atactic cyclopentane polymer and Formula IV represents an isotactic cyclopentane polymer formed by the reaction as shown in Formula II. ##STR5##

For these polymers, a new notation is used to identify their stereochemistry. This system is based on the common mr formalism for vinyl polymers, where capital letters refer to relative stereochemistry within the ring and lower-case letters refer to relative stereochemistry between the rings. M(m) refers to a meso stereochemical relationship between vicinal stereogenic centers and R(r) refers to a racemic relationship.

In the presence of the achiral metallocene derivatives Cp2 MX2 (M=Zr, Hf; X=Cl, Me), an unprecedented trans selectivity is observed in the cyclopolymerization of 1,5-hexadiene. This trans selectivity is temperature dependent. At a polymerization temperature of 80 C., 13 C-NMR analysis indicates that there is a 1:1 ratio between trans and cis five-membered rings. At a polymerization temperature of 25 C., approximately 80% of the cyclopentane rings in the polymer are trans. Polymerization at -80 C. afforded the first example of polymethylene-trans-1,3-cyclopentane (95% trans by 13 C-NMR). The 13 C-NMR spectra of these polymers allow confirmation of the 13 C-NMR assignments of Cheng, supra, and provide considerable additional information on the microstructure of these polymers. In particular, the 13 C resonance at 38.5 ppm, assigned to C2 of the five-membered ring, exhibits fine structure which can be attributed to mRm, mRr, and rRr tetrads. Resonances at 33.1 and 31.6 ppm appear as two peaks in equal ratios which are assigned as the mR, rR and rM, mM triads, respectively. According to this analysis, the microstructure of this polymer is assigned as the trans, atactic polymer. The trans selectivity in the presence of the achiral catalyst is attributable to an unfavorable steric interaction between the growing polymer chain and one Cp ring when a Re--Re or Si--Si sequence of insertion-cyclization occurs. For the formation of the cis ring, the polymer chain is forced into the Cp ligands; for the formation of the trans ring, the polymer chain is directed away from the Cp ligands.

Polymerization of 1,5-hexadiene in toluene in the presence of the chiral precursor EBIZrCl2 proceeds with much higher conversion of the monomer after one hour to give a high molecular weight solid polymer. This catalyst exhibits lower trans selectivity (64% trans at 22 C.; 61% at 50 C.) but proceeds at a greater rate than the achiral metallocene derivatives Cp2 ZrX2. 13 C-NMR analysis is consistent with an isotactic structure (for the cyclopolymer, tacticity refers to the relative stereochemistry of the cyclopentane rings, not necessarily the relative stereochemistry of adjacent substituents). The isotactic structure was as expected for this isospecific catalyst given that polymerization of propylene with the isospecific catalyst EBIZrCl2 produces isotactic polypropylene. In particular, 13 C resonances at 33.1 (mR, rR) and 31.6 (rM, mM) now appear as two peaks in unequal ratios. The presence of these peaks, and their relative intensities, is consistent with an isotactic 60% trans/40% cis microstructure.

The lower trans selectivity in the presence of EBIZrCl2 is attributable to competitive double diastereodifferentiation in the cyclopolymerization. These catalysis are isospecific; they favor polymerization of the same enantioface of the olefin. For a diolefin, isospecificity should favor a cis ring fusion. Thus, for the isospecific EBIZrCl2 catalysts, the inherent diastereoselectivity of the cyclization reaction should favor a trans ring fusion whereas the isospecificity of the coordination sites should favor a cis ring fusion. These two competing factors could thus explain the lower trans selectivity.

It is to be understood that while the invention has been described above in conjunction with preferred specific embodiments, the description and examples are intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3357961 *May 24, 1965Dec 12, 1967Exxon Research Engineering CoCopolymers of ethylene and hexadiene 1, 5
US3435020 *Mar 7, 1958Mar 25, 1969Hercules IncCrystalline polymers of alpha,omega-diolefins
US3472830 *May 27, 1958Oct 14, 1969Du PontPolymerization of unconjugated alkadienes into linear polymers
US4360551 *Jun 19, 1981Nov 23, 1982Mobil Oil CorporationFlexible film laminate especially adapted for use in the construction of a retortable food pouch
US4391738 *Jan 28, 1982Jul 5, 1983Exxon Research And Engineering Co.Catalyst for olefinic polymerization
US4404344 *Feb 27, 1981Sep 13, 1983Basf AktiengesellschaftPreparing ethylene polymers using Ziegler catalyst comprising cyclodienyl compound of zirconium
US4769510 *Nov 25, 1985Sep 6, 1988Hoechst AktiengesellschaftProcess for the preparation of polyolefins
US4794096 *Sep 11, 1987Dec 27, 1988Fina Technology, Inc.Hafnium metallocene catalyst for the polymerization of olefins
US4808561 *Mar 18, 1988Feb 28, 1989Exxon Chemical Patents Inc.Supported polymerization catalyst
US4897455 *Dec 2, 1988Jan 30, 1990Exxon Chemical Patents Inc.Polymerization process
US4931526 *Nov 10, 1988Jun 5, 1990Mitsui Petrochemical Industries, Ltd.α-olefinic random copolymer and production process thereof
EP0273655A2 *Dec 18, 1987Jul 6, 1988Exxon Chemical Patents Inc.Ethylene copolymers
EP0284707A1 *Sep 21, 1987Oct 5, 1988Fina Technology, Inc.Hafnium metallocene catalyst for the polymerization of olefins
EP0311299A1 *Sep 29, 1988Apr 12, 1989Toa Nenryo Kogyo Kabushiki KaishaA diolefin polymer or copolymer and a process for the production of the same
EP0358103A1 *Aug 31, 1989Mar 14, 1990Idemitsu Kosan Company LimitedMethod for the preparation of a polymer
EP0390490A1 *Mar 27, 1990Oct 3, 1990Tonen CorporationUse of a hexadienepolymer and process for its preparation
EP0390491A1 *Mar 27, 1990Oct 3, 1990Tonen Corporation1,4-pentadiene polymer and process for preparation of a 1,4- pentadiene polymer
EP0390492A1 *Mar 27, 1990Oct 3, 1990Tonen CorporationOctadiene polymer and process for producing the same
EP0390493A1 *Mar 27, 1990Oct 3, 1990Tonen CorporationHeptadiene polymer and process for producing the same
EP1358103A1 *Jan 24, 2002Nov 5, 2003Denis Philippe BaronAdjustable keel for sailboats
Non-Patent Citations
Reference
1Arcus, "The Stereoisomerism of Addition Polymers. Part I. The Stereochemistry of Addition and Configurations of Maximum Order," J. Amer. Chem. Soc., 1955, pp. 2801-2806.
2 *Arcus, The Stereoisomerism of Addition Polymers. Part I. The Stereochemistry of Addition and Configurations of Maximum Order, J. Amer. Chem. Soc., 1955, pp. 2801 2806.
3Cheng and Khasat, "13 C-NMR Characterization of Poly(1,5-hexadiene)", J. Appl. Polymer Sci., vol. 35, 1988, pp. 825-829.
4 *Cheng and Khasat, 13 C NMR Characterization of Poly(1,5 hexadiene) , J. Appl. Polymer Sci., vol. 35, 1988, pp. 825 829.
5Coates and Waymouth, "Enantioselective Cyclopolymerization: Optically Active Poly(methylene-1,3-cyclopentane)", J. of Am. Chem. Soc., 113, 6270-6271 (1991).
6 *Coates and Waymouth, Enantioselective Cyclopolymerization: Optically Active Poly(methylene 1,3 cyclopentane) , J. of Am. Chem. Soc., 113, 6270 6271 (1991).
7Ewen et al., "Syndiospecific Propylene Polymerization with Group 4 Metallocenes", J. Am. Chem. Soc., 110, 1988, pp. 6255-6256.
8 *Ewen et al., Syndiospecific Propylene Polymerization with Group 4 Metallocenes , J. Am. Chem. Soc., 110, 1988, pp. 6255 6256.
9Ewen, "Mechanisms of Stereochemical Control in Propylene Polymerizations with Soluble Group 4B Metallocene/Methylalumoxane Catalysts", J. Am. Chem. Soc., 106, 194, pp. 6355-6364.
10 *Ewen, Mechanisms of Stereochemical Control in Propylene Polymerizations with Soluble Group 4B Metallocene/Methylalumoxane Catalysts , J. Am. Chem. Soc., 106, 194, pp. 6355 6364.
11Farina, "The Stereochemistry of Linear Macromolecules", Top. Stereochem., 17, 1987, pp. 1-111.
12 *Farina, The Stereochemistry of Linear Macromolecules , Top. Stereochem., 17, 1987, pp. 1 111.
13Kaminsky et al., "Polymerization of Propene and Butene with a Chiral Zirocene and Methylalumoxane as Catalyst", Angew. Chem. Int. Ed. Engl., 24:6, 1965, pp. 507-508.
14 *Kaminsky et al., Polymerization of Propene and Butene with a Chiral Zirocene and Methylalumoxane as Catalyst , Angew. Chem. Int. Ed. Engl., 24:6, 1965, pp. 507 508.
15Makowski et al., "1,5-Hexadiene Polymers. I. Structure and Properties of Poly-1,5-Hexadiene", J. Polymer Sci.: Part A, vol. 2, 1964, pp. 1549-1566.
16 *Makowski et al., 1,5 Hexadiene Polymers. I. Structure and Properties of Poly 1,5 Hexadiene , J. Polymer Sci.: Part A, vol. 2, 1964, pp. 1549 1566.
17 *Makowski et al., J. Polymer Sci, Part A, Z , 1549, 1964.
18Makowski et al., J. Polymer Sci, Part A, Z, 1549, 1964.
19Marvel et al., "Intermolecular Intramolecular Polymerization of α-Olefins by Metal Alkyl Coordination Catalysts", J. Am. Chem. Soc., 80, Apr.-Jun. 1958, pp. 1740-1744.
20 *Marvel et al., Intermolecular Intramolecular Polymerization of Olefins by Metal Alkyl Coordination Catalysts , J. Am. Chem. Soc., 80, Apr. Jun. 1958, pp. 1740 1744.
21 *Marvel et al., J. Am. Chem. Soc., 1958, 80, 1970.
22Resconi and Waymouth, "Diastereoselectivity in the Homogeneous Cyclopolymerization of 1,5-Hexadiene", J. of Am. Chem. Soc., 112, 4953-4954 (1990).
23 *Resconi and Waymouth, Diastereoselectivity in the Homogeneous Cyclopolymerization of 1,5 Hexadiene , J. of Am. Chem. Soc., 112, 4953 4954 (1990).
24Schleyer et al., "The Evaluation of Strain in Hydrocarbons. The Strain in Adamantane and Its Origin", J. Am. Chem. Soc., 92:8, Apr. 22, 1970, pp. 2377-2386.
25 *Schleyer et al., The Evaluation of Strain in Hydrocarbons. The Strain in Adamantane and Its Origin , J. Am. Chem. Soc., 92:8, Apr. 22, 1970, pp. 2377 2386.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5332706 *Dec 28, 1992Jul 26, 1994Mobil Oil CorporationProcess and a catalyst for preventing reactor fouling
US5455741 *Oct 26, 1993Oct 3, 1995Pulse Engineering, Inc.Holder for mounting an electronic element
US5473028 *Apr 19, 1994Dec 5, 1995Mobil Oil CorporationProcess and a catalyst for preventing reactor fouling
US5495035 *Jun 1, 1994Feb 27, 1996University Of Iowa Research FoundationReacting an ansa-bis-cyclopentadiene compound with a metal amide complex
US5525678 *Sep 22, 1994Jun 11, 1996Mobil Oil CorporationProcess for controlling the MWD of a broad/bimodal resin produced in a single reactor
US5578743 *Apr 4, 1995Nov 26, 1996Mobil Oil CorporationCyclopymerization polymers from non-conjugated dienes
US5597935 *May 15, 1995Jan 28, 1997University Of Iowa Research FoundationSynthesis of ansa-metallocene catalysts
US5602067 *Nov 3, 1994Feb 11, 1997Mobil Oil CorporationSupported alumoxane activated with metallocene
US5608019 *Nov 8, 1993Mar 4, 1997Mobil Oil CorporationTemperature control of MW in olefin polymerization using supported metallocene catalyst
US5614456 *Nov 3, 1994Mar 25, 1997Mobil Oil CorporationCatalyst for bimodal molecular weight distribution ethylene polymers and copolymers
US5882750 *Jul 3, 1995Mar 16, 1999Mobil Oil CorporationSingle reactor bimodal HMW-HDPE film resin with improved bubble stability
US6005463 *Jan 30, 1997Dec 21, 1999Pulse EngineeringThrough-hole interconnect device with isolated wire-leads and component barriers
US6037296 *Apr 24, 1998Mar 14, 2000Mobil Oil CorporationComonomer pretreated bimetallic catalyst for blow molding and film applications
US6051525 *Jul 14, 1997Apr 18, 2000Mobil CorporationCatalyst for the manufacture of polyethylene with a broad or bimodal molecular weight distribution
US6207608Aug 9, 1996Mar 27, 2001University Of Iowa Research FoundationOlefin polymerization with direct use of ansa-metallocene amide complexes as catalysts
US6417130Mar 25, 1996Jul 9, 2002Exxonmobil Oil CorporationSlurrying a hydroxyl group, a hydrocarbon solvent, an organo magnesium compound, an alcohol, a metallocene and alumoxane then removing solvent
US6454989Nov 10, 1999Sep 24, 2002Kimberly-Clark Worldwide, Inc.Process of making a crimped multicomponent fiber web
US6486089Nov 9, 1995Nov 26, 2002Exxonmobil Oil CorporationBimetallic catalyst for ethylene polymerization reactions with uniform component distribution
US6613704 *Oct 12, 2000Sep 2, 2003Kimberly-Clark Worldwide, Inc.Continuous filament composite nonwoven webs
US6699955 *Nov 14, 2000Mar 2, 2004E. I. Du Pont De Nemours And CompanyCopolymerization of ethylene and dienes
US6713425Jun 3, 2002Mar 30, 2004Univation Technologies, LlcOne pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerization
US6727321Jun 27, 2000Apr 27, 2004University Of AkronAllylation poly(vinyl chloride) and further functionalization of allyl groups
US6740617Jun 3, 2002May 25, 2004Univation Technologies, LlcUsing as catalysts metallocene complex and trialkylaluminum compound, wherein metallocene complex contains one or two substituted or unsubstituted cyclopentadienyl groups and transition metal selected from titanium, zirconium and hafnium
US6777056Oct 12, 2000Aug 17, 2004Kimberly-Clark Worldwide, Inc.Regionally distinct nonwoven webs
US6831133Dec 8, 2000Dec 14, 2004The University Of AkronAddition of unsaturated hydrocarbons to poly(vinyl chloride) and functionalization thereof
US6855654Sep 16, 2002Feb 15, 2005Exxonmobil Oil CorporationBimetallic catalyst for ethylene polymerization reactions with uniform component distribution
US7101939Oct 11, 2002Sep 5, 2006Exxonmobil Chemical Patents Inc.Ethylene/α-olefin copolymer made with a non-single-site/single-site catalyst combination, its preparation and use
US7790810Jun 6, 2005Sep 7, 2010Cornell Research Foundation, Inc.monodisperse block polymer prepared by living insertion/cyclization/ring-opening polymerization with 2,1-insertion catalyst; 1,5-hexadiene and propylene; polymer has 3-vinyltetramethylene units and methylene-1,3-cyclopentane units; for tires by crosslinking the pendant vinyl groups with sulfur
WO1995006669A1 *Aug 23, 1994Mar 9, 1995Mobil Oil CorpNovel cyclopolymerization polymers from non-conjugated dienes
WO2000028123A1Nov 12, 1999May 18, 2000Kimberly Clark CoCrimped multicomponent fibers and methods of making same
WO2004067589A1 *Jan 24, 2003Aug 12, 2004Geoffrey W CoatesVinyl functional olefin polymers
Classifications
U.S. Classification526/164, 526/336, 526/340.2, 526/308, 502/117, 526/160, 526/335, 526/340.3, 526/943
International ClassificationC08F36/20, C08G61/00
Cooperative ClassificationY10S526/943, C08F36/20, C08G61/00
European ClassificationC08G61/00, C08F36/20
Legal Events
DateCodeEventDescription
Jul 15, 1997FPExpired due to failure to pay maintenance fee
Effective date: 19970507
May 4, 1997LAPSLapse for failure to pay maintenance fees
Dec 10, 1996REMIMaintenance fee reminder mailed
Jul 11, 1995CCCertificate of correction